Obviously lighting and getting exposure right in camera is your first priority and is the most important. And yes, you can achieve that lighting or very similar lighting with natural light using a window with the right natural light circumstances. Not all windows can provide that light obviously and you may have to wait for a certain time of day. Not all photographers are willing to do this. If you aren't, use a beauty dish and strobe.
Secondly what's important is editing. You need to learn how to use adjustment layers. This is highly important, as it is a non-destructive way to edit that gives you a lot of freedom to make adjustments to any color, contrast and exposure adjustments that you make without permanently changing the background image. The main adjustment layer options that you should learn are: Curves, Selective Color, and Hue/saturation. I use curves to get that contrast. I use selective color to control the colors on all color-channels of the image. I use hue/saturation to desaturate the image a little bit, as adding contrast tends to make an image too vibrant in my personal opinion. I guarantee you that you can get those results using these tools, but you're going to have to study, experiment and practice in order to get results like what are in that image. It's taken me 3 years to even begin to master the editing technique that I use now. Start by looking up tutorials on youtube. Your search results may not give you all of the answers you need. If you want a more extensive explanation on how to use these tools in photoshop, I recommend acquiring some classes on Creative Live, particularly the Fashion Photography 101 with Lara Jade. You may have to pay for this content, but sometimes you have to invest in your skillset. It's just like paying for your gear, only in my opinion this is a much more worthy investment.
